US3997383A - Cross-linked amide/olefin polymeric laminates - Google Patents

Cross-linked amide/olefin polymeric laminates Download PDF

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Publication number
US3997383A
US3997383A US05/556,755 US55675575A US3997383A US 3997383 A US3997383 A US 3997383A US 55675575 A US55675575 A US 55675575A US 3997383 A US3997383 A US 3997383A
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United States
Prior art keywords
layer
laminate
adhesive
olefin
coextruded
Prior art date
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Expired - Lifetime
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US05/556,755
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English (en)
Inventor
Anne C. Bieler
Henry G. Schirmer
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WR Grace and Co Conn
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WR Grace and Co
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Publication date
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Priority to US05/556,755 priority Critical patent/US3997383A/en
Priority to CA237,971A priority patent/CA1051821A/fr
Priority to GB9047/76A priority patent/GB1480204A/en
Priority to DE19762609352 priority patent/DE2609352A1/de
Priority to SE7603086A priority patent/SE7603086L/xx
Priority to FR7606563A priority patent/FR2309333A1/fr
Priority to AU11768/76A priority patent/AU496808B2/en
Priority to IT20973/76A priority patent/IT1056950B/it
Priority to JP51024714A priority patent/JPS5918223B2/ja
Priority to US05/689,440 priority patent/US4104404A/en
Application granted granted Critical
Publication of US3997383A publication Critical patent/US3997383A/en
Assigned to W.R. GRACE & CO.-CONN, A CORP. OF CT reassignment W.R. GRACE & CO.-CONN, A CORP. OF CT MERGER (SEE DOCUMENT FOR DETAILS). MAY 25, 1988 Assignors: GRACE MERGER CORPORATION, W.R. GRACE & CO.
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
    • B29C71/04—After-treatment of articles without altering their shape; Apparatus therefor by wave energy or particle radiation, e.g. for curing or vulcanising preformed articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a non-planar shape
    • B32B1/08—Tubular products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
    • B29C2035/0844—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using X-ray
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
    • B29C2035/085—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using gamma-ray
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0866—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using particle radiation
    • B29C2035/0872—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using particle radiation using ion-radiation, e.g. alpha-rays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/06—PE, i.e. polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2323/00—Polyalkenes
    • B32B2323/04—Polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2323/00—Polyalkenes
    • B32B2323/04—Polyethylene
    • B32B2323/046—LDPE, i.e. low density polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2377/00—Polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1334—Nonself-supporting tubular film or bag [e.g., pouch, envelope, packet, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31536—Including interfacial reaction product of adjacent layers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31725—Of polyamide
    • Y10T428/31739—Nylon type
    • Y10T428/31743—Next to addition polymer from unsaturated monomer[s]
    • Y10T428/31746—Polymer of monoethylenically unsaturated hydrocarbon
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31725—Of polyamide
    • Y10T428/3175—Next to addition polymer from unsaturated monomer[s]
    • Y10T428/31757—Polymer of monoethylenically unsaturated hydrocarbon
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31909—Next to second addition polymer from unsaturated monomers
    • Y10T428/31913—Monoolefin polymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31909—Next to second addition polymer from unsaturated monomers
    • Y10T428/31928—Ester, halide or nitrile of addition polymer

Definitions

  • This invention relates to laminated films in tubular and sheet configurations for packaging, cooking, and storing food. Particularly, the invention relates to laminates having polyamide and polyolefin layers, specifically nylon and polyethylene layers.
  • Laminates of nylon and polyethylene are widely used for packaging various products and have been found especially suitable for foodstuff containing packages such as bags or pouches subjected to widely varying temperatures and conditions.
  • Nylon is used for such packages because it is an oxygen barrier, has a high melting point, and is strong and clear.
  • Polyethylene is used as an inner surface for such laminates because it is easily heat sealable, is moisture impermeable, and is relatively chemically inert to many food stuffs.
  • nylon is principally its high cost, moisture permeability, and poor heat sealability; but, these disadvantages are largely offset by polyethylene's low cost, low moisture permeability, and good heat sealability. While the complimentary characteristics of nylon and polyethylene make them suitable for use as laminates, especially for packages containing food, the materials are somewhat incompatible because they are considerably difficult to initially bond together. This difficulty is thought to be attributable to their differences in physical and chemical structures. Also, once joined, the two materials will often separate upon physical deformation, particularly when agitated at water cooking temperatures which generally range from 140° F upwardly.
  • a number of techniques have been developed in an attempt to overcome the bonding difficulties of nylon to polyethylene. These techniques include chemically and electrically treating the surface of the polyethylene and the incorporation of a layer of adhesive between the nylon and polyethylene. Some of the adhesives used in the prior art are ethylene-acrylic acid copolymers and the zinc or magnesium neutralized ionic copolymers known as ionomers. Even blends of an ionomer and polyethylene have been used in an attempt to find an adhesive that maintains sufficient cohesion in hot water or at boiling water temperatures.
  • amide/olefin polymeric laminates tend to delaminate and shred within a short period of time. Accordingly, it is a principal object of the present invention to provide an amide/olefin polymeric laminate which will not delaminate under physical deformation at elevated temperatures.
  • this invention is a method of making a laminate which will resist delamination and shredding in an elevated temperature medium.
  • the laminate is formed by coextruding an amide polymer and an olefin polymer with an adhesive having cross-linkable monomeric units disposed therebetween.
  • the adhesive is preferably composed predominately of olefin units.
  • the coextruded laminate is cross-linked by ionizing radiation in the dosage range of 6 to 10 MR. Higher dosages could be used but are not necessary and are uneconomical.
  • the invention is a method of producing an olefin/amide laminate for prolonged use in elevated temperature media in which the method comprises the steps of: coextruding a tubular laminate having polyamide and irradiatively cross-linkable polyolefin layers with an adhesive disposed between the polyolefin and polyamide layers, the major component of the adhesive being olefin units which are cross-linkable by radiation; cooling and flattening the tubular laminate; and, irradiating the laminate by ionizing radiation to a dosage level in the range of 6 to 10 MR.
  • the present invention is a laminated film which comprises a polyamide layer; a polyolefin layer; an adhesive disposed between said polyamide and polyolefin layers, the major component of the adhesive being olefin units; and, the laminate being cross-linked to the equivalent of an irradiation dosage in the range of 6 to 10 MR.
  • the olefin is ethylene so that the preferred polyolefin layer is polyethylene and the preferred adhesive is an ionomer in which ethylene is the predominate monomeric unit.
  • the polyolefin layer may be an ethylene vinyl acetate copolymer and the adhesive may comprise an acid copolymer resin.
  • Polymer includes homopolymers, polymers, copolymers, terpolymers, and block, graft, random, or alternating polymers.
  • Ionomer means a polymer which has ethylene as its major component but has both covalent and ionic bonds.
  • the anions hang from the hydrocarbon chain and the cations are metallic, e.g. magnesium or zinc so that ionomers may sometimes be referred to as a zinc neutralized ionic copolymer.
  • Adhesive means a polymeric substance capable of bonding two polymeric film layers together and for this application specifically refers to resins comprising ionomers and blends thereof with polyolefins and to acid copolymer resins and blends thereof with polyolefin resins.
  • Amide or amide polymer means a nylon selected from the group consisting of polycaproamide, polyhexamethylene, adipamide, polyhexamethylene sebacamide, polycaprylamide, polyundecanoamide, and polydodecanamide. These nylons are respectively commonly known as nylon-6; nylon-6, 6; nylon 6, 10; nylon 8; nylon 11; and nylon 12 with the preferred nylon being nylon-6 such as type 8207 which is sold by Allied Chemical Corporation.
  • Olefin means the group of unsaturated hydrocarbons of the general formula C n H 2n and includes ethylene, propylene, butene-1, etc., and blends thereof.
  • the olefins of interest are the mono-alpha olefins having 2 to 8 carbon atoms and which cross-link when exposed to ionizing radiation.
  • Irradiation means exposure to high energy radiation such as electrons, X-rays, gamma rays, beta rays, etc. which induce cross-linking between the molecules of the irradiated material.
  • irradiation is carried out by an electron accelerator and the dosage levels is determined by the insoluble gel in the irradiated material.
  • the dosage is measured in rads wherein one rad is the absorbed dose of ionizing radiation equal to an energy of 100 ergs per gram of irradiated material.
  • a megarad (MR) is one million rads.
  • a tubular casing which is 10 inches wide in the flattened condition and which has a 4.5 mil thickness was manufactured by a coextrusion process.
  • a coextrusion die fed by four extruders divided the melt streams into ten separate layers. Beginning from the inside of the tube, the first two layers were polyethylene having a density of 0.92 gms./cc. These two layers were fed from a 31/2 inch Hartig extruder and the two layers had a combined extruded thickness of 1.2 mils.
  • Next to the inner polyethylene layers was the first adhesive layer with the adhesive being an ionomer resin fed from a 11/2 inch MPM extruder and the thickness of the first adhesive layer was 0.3 mils.
  • Adjacent to the nylon layers was a second adhesive layer fed from the same extruder as the first layer and having the same thickness of 0.3 mils.
  • the outer two layers were the same polyethylene as the first two layers except that the die for the outer two layers was fed from a 13/4 inch Prodex extruder and the total thickness of these two layers was 1.2 mils.
  • the polyethylene and the ionomer were products of E. I. du Pont de Nemours & Co. of Wilmington, Delaware, the polyethylene being PE-2650 and the ionomer being Surlyn 1650.
  • the nylon resin was nylon 6, type 8207 from Allied Chemical Corp. of Morristown, N.J.
  • the complete laminate has a structure as follows: polyethylene/polyethylene/ionomer/nylon/nylon/nylon/nylon/ionomer/polyethylene/polyethylene.
  • the unit layer has adhesive on either side and to the respective adhesive layers are applied the polyethylene unit layers which consist of sublayers.
  • one polyethylene layer forms the inner surface of the tubing and one of the other polyethylene layers forms the outer surface of the tubing.
  • Multilayer tubings as described immediately above were irradiated to different dosage levels and then each tubing was cut into 5 tubular sections or casings and one end of each casing was closed with a U-shaped metal clip. Each casing was then filled with 1 cup vegetable oil and 5 quarts of water, closed with a clip, and tumbled in water at 190° F. The tumbling was accomplished by placing the filled casings in a modified, front loading, commercial laundry machine which was filled with the heated water. Placing the casings in the water initially cooled the water to about 172° F. After about 20 minutes the water again reached 190° F and agitation began with the following results:
  • a portion of the preferred tubing was irradiated to a dosage of approximately 8 MR and then both irradiated and nonirradiated tubing was cut in 30 inch lengths and closed at one end with a U-shaped metal clip to form a casing.
  • the casings were then filled with three representative products, these being (1) a mixture of 20% vegetable oil with water as it was known that the ionomer/polyethylene bond is weakened by fatty substances; (2) creamed carrots; (3) macaroni and cheese. All of the casings were hand filled with five quarts of the test product and sealed with a clip after expressing excess air by hand.
  • a modified laundry machine of the horizontal rotating drum, front loading type with a capacity of 125 lbs.
  • the practical significance of a test like the foregoing is that in certain institutional food cooking processes it has been discovered that food products may be cooked in casings and, after cooling, the food may be stored unfrozen at a temperature in the range of 28° to 32° F. In these institutional cooking processes, it has been found quite advantageous to tumble the filled casings in heated water thus increasing the transfer of heat into the food product within the casing and thereby reducing the cooking time. In like manner, after cooking, the food may be rapidly cooled to its storage temperature by tumbling and agitation in cooled water. By making it possible for the temperature of the food to be reduced quickly from its cooking temperature to its storage temperature the growth of microorganisms can be effectively restricted thus increasing the storage lifetime of the food and enhancing its quality.
  • the irradiated casings according to the present invention are the only thermoplastic packaging materials which have been found to be satisfactory for the above described cooking and storage process.
  • a commercial electron accelerator was the radiation unit used to irradiate the polyethylene/nylon/polyethylene laminate described hereinabove, and it was found that it was necessary to irradiate the laminate to a dosage of at least 6 MR. Increased dosage levels could be used but would be uneconomical as no increase in resistance to delamination and shredding was observed for the higher dosage levels.
  • the increased abuse resistance and resistance to delamination is thought to be possibly due to irradiation induced cross-linking at and across the polyethylene/ionomer interface and the ionomer/nylon interface as there is some commingling of the melts in the coextruded laminate, to increased melting temperature of the cross-linked adhesive, and to increased strength in the polyethylene layers because of cross-linking.
  • this invention is not limited to any particular theory explaining the increased resistance to delamination.
  • high density polyethylene may be used as one or both of the polyethylene layers or an ethylene vinyl acetate copolymer may be used for one or both of the polyethylene layers.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Wrappers (AREA)
US05/556,755 1975-03-10 1975-03-10 Cross-linked amide/olefin polymeric laminates Expired - Lifetime US3997383A (en)

Priority Applications (10)

Application Number Priority Date Filing Date Title
US05/556,755 US3997383A (en) 1975-03-10 1975-03-10 Cross-linked amide/olefin polymeric laminates
CA237,971A CA1051821A (fr) 1975-03-10 1975-10-20 Pellicules stratifiees de type olefine-amide reticulee
GB9047/76A GB1480204A (en) 1975-03-10 1976-03-05 Laminates of nylon and olefin polymers their preparation and use in packaging
DE19762609352 DE2609352A1 (de) 1975-03-10 1976-03-06 Schichtfolie und verfahren zu deren herstellung
FR7606563A FR2309333A1 (fr) 1975-03-10 1976-03-08 Stratifies de nylon et de polymeres d'olefines, utilisables comme matiere d'emballage
AU11768/76A AU496808B2 (en) 1975-03-10 1976-03-08 Laminates of nylon and olefin polymers their preparation and use in packaging
SE7603086A SE7603086L (sv) 1975-03-10 1976-03-08 Laminat av nylon- och olefinpolymerer, deras framstellning och anvendning vid forpackning
IT20973/76A IT1056950B (it) 1975-03-10 1976-03-08 Laminato di superpoliamide e polilimeri olefinici sua prepparazione e suo impiego per il confezionamento di prodotti
JP51024714A JPS5918223B2 (ja) 1975-03-10 1976-03-09 ナイロンとオレフイン重合体のフイルム積層品
US05/689,440 US4104404A (en) 1975-03-10 1976-05-24 Cross-linked amide/olefin polymeric tubular film coextruded laminates

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CA (1) CA1051821A (fr)
DE (1) DE2609352A1 (fr)
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US4095012A (en) * 1974-12-23 1978-06-13 W. R. Grace & Co. Oriented nylon and laminates thereof
US4101711A (en) * 1977-03-18 1978-07-18 Champion International Corporation Bone resistant packaging material
US4104404A (en) * 1975-03-10 1978-08-01 W. R. Grace & Co. Cross-linked amide/olefin polymeric tubular film coextruded laminates
US4169910A (en) * 1978-06-28 1979-10-02 Union Carbide Corporation Multilayer film including polyolefin layers and a polybutylene layer useful for the production of bags
US4197326A (en) * 1978-07-22 1980-04-08 Mitsubishi Plastics Industries Limited Processed meat packaging tube and method of packaging
US4215176A (en) * 1978-09-05 1980-07-29 Allied Chemical Corporation Polyamide laminates
EP0015775A1 (fr) * 1979-03-12 1980-09-17 Mobil Oil Corporation Sachets laminés thermoplastiques fabriqués par co-extrusion
US4274900A (en) * 1978-08-30 1981-06-23 W. R. Grace & Co. Multi-layer polyester/polyolefin shrink film
US4289727A (en) * 1979-12-19 1981-09-15 Mobil Oil Corporation Method for extrusion of tubular films
US4309466A (en) * 1979-12-17 1982-01-05 Champion International Corporation Flexible laminated packaging material comprising metallized intermediate layer
US4606922A (en) * 1983-04-21 1986-08-19 W. R. Grace & Co., Cryovac Div. Cook-in meat packaging
US4654240A (en) * 1984-09-28 1987-03-31 Baxter Travenol Laboratories, Inc. Laminate film for flexible containers
US4686125A (en) * 1984-09-28 1987-08-11 Baxter Travenol Laboratories, Inc. Film laminate for sterile flexible containers
US4687688A (en) * 1986-02-18 1987-08-18 American Can Company Oriented multiple layer films and bags made therefrom
US4692361A (en) * 1984-09-28 1987-09-08 Baxter Travenol Laboratories, Inc. Film laminate with gas barrier for sterile flexible containers
US5567489A (en) * 1993-09-16 1996-10-22 The Dow Chemical Company Multilayer halogen-free barrier film for ostomy and transdermal drug delivery applications
US5620649A (en) * 1989-11-29 1997-04-15 Cordis Corporation Puncture resistant balloon catheter
US5976288A (en) * 1997-01-10 1999-11-02 Ekendahl; Lars O. Method of forming a molded, multi-layer structure
US7073309B2 (en) 2003-03-12 2006-07-11 Avery Dennison Corporation Method of using a reusable closure for packages
WO2007038850A1 (fr) * 2005-10-03 2007-04-12 Unipac Embalagens Ltda Pellicule polymère, procédé d’obtention et de traitement d’une pellicule polymère, et emballage

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Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4095012A (en) * 1974-12-23 1978-06-13 W. R. Grace & Co. Oriented nylon and laminates thereof
US4104404A (en) * 1975-03-10 1978-08-01 W. R. Grace & Co. Cross-linked amide/olefin polymeric tubular film coextruded laminates
US4101711A (en) * 1977-03-18 1978-07-18 Champion International Corporation Bone resistant packaging material
US4169910A (en) * 1978-06-28 1979-10-02 Union Carbide Corporation Multilayer film including polyolefin layers and a polybutylene layer useful for the production of bags
US4197326A (en) * 1978-07-22 1980-04-08 Mitsubishi Plastics Industries Limited Processed meat packaging tube and method of packaging
US4274900A (en) * 1978-08-30 1981-06-23 W. R. Grace & Co. Multi-layer polyester/polyolefin shrink film
US4215176A (en) * 1978-09-05 1980-07-29 Allied Chemical Corporation Polyamide laminates
EP0015775A1 (fr) * 1979-03-12 1980-09-17 Mobil Oil Corporation Sachets laminés thermoplastiques fabriqués par co-extrusion
US4309466A (en) * 1979-12-17 1982-01-05 Champion International Corporation Flexible laminated packaging material comprising metallized intermediate layer
US4289727A (en) * 1979-12-19 1981-09-15 Mobil Oil Corporation Method for extrusion of tubular films
US4606922A (en) * 1983-04-21 1986-08-19 W. R. Grace & Co., Cryovac Div. Cook-in meat packaging
US4654240A (en) * 1984-09-28 1987-03-31 Baxter Travenol Laboratories, Inc. Laminate film for flexible containers
US4686125A (en) * 1984-09-28 1987-08-11 Baxter Travenol Laboratories, Inc. Film laminate for sterile flexible containers
US4692361A (en) * 1984-09-28 1987-09-08 Baxter Travenol Laboratories, Inc. Film laminate with gas barrier for sterile flexible containers
US4687688A (en) * 1986-02-18 1987-08-18 American Can Company Oriented multiple layer films and bags made therefrom
US4767651A (en) * 1986-02-18 1988-08-30 American National Can Company Multiple layer film and containers made therefrom
US5620649A (en) * 1989-11-29 1997-04-15 Cordis Corporation Puncture resistant balloon catheter
US5567489A (en) * 1993-09-16 1996-10-22 The Dow Chemical Company Multilayer halogen-free barrier film for ostomy and transdermal drug delivery applications
US5976288A (en) * 1997-01-10 1999-11-02 Ekendahl; Lars O. Method of forming a molded, multi-layer structure
US7073309B2 (en) 2003-03-12 2006-07-11 Avery Dennison Corporation Method of using a reusable closure for packages
US7629046B2 (en) 2003-03-12 2009-12-08 Avery Dennison Corporation Reusable closures for packages and methods of making and using the same
WO2007038850A1 (fr) * 2005-10-03 2007-04-12 Unipac Embalagens Ltda Pellicule polymère, procédé d’obtention et de traitement d’une pellicule polymère, et emballage
US20090047455A1 (en) * 2005-10-03 2009-02-19 Angel Visentim Ortiz Polymeric Film, a Process for Obtaining and Treating a Polymeric Film, and a Package

Also Published As

Publication number Publication date
FR2309333A1 (fr) 1976-11-26
US4104404A (en) 1978-08-01
IT1056950B (it) 1982-02-20
DE2609352A1 (de) 1976-09-23
GB1480204A (en) 1977-07-20
CA1051821A (fr) 1979-04-03
FR2309333B3 (fr) 1978-12-15
AU496808B2 (en) 1978-11-02
JPS51112888A (en) 1976-10-05
JPS5918223B2 (ja) 1984-04-26
AU1176876A (en) 1977-09-15
SE7603086L (sv) 1976-09-13

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